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EP0154867B1 - Dérivés de 1,3-butadiène 2-substituée et procédé de leur préparation - Google Patents

Dérivés de 1,3-butadiène 2-substituée et procédé de leur préparation Download PDF

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EP0154867B1
EP0154867B1 EP85101980A EP85101980A EP0154867B1 EP 0154867 B1 EP0154867 B1 EP 0154867B1 EP 85101980 A EP85101980 A EP 85101980A EP 85101980 A EP85101980 A EP 85101980A EP 0154867 B1 EP0154867 B1 EP 0154867B1
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carbon atoms
compound
formula
substituted
halogen
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EP0154867A1 (fr
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Fumie Sato
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority claimed from JP59033733A external-priority patent/JPS60197694A/ja
Priority claimed from JP27715484A external-priority patent/JPS61151196A/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages

Definitions

  • This invention relates to novel butadiene derivatives and more particularly, to novel 2-substituted-1,3-butadiene compounds.
  • the invention also relates to a process for producing the novel compounds.
  • 2-triethylsilyl-1,3-butadiene is prepared by a process which comprises the steps of reacting 1,4-dichloro-2-butyne and triethylsilane to obtain 2-triethylsilyl-1,4-dichloro-2-butene, and subjecting the butene to dechlorination in an alcohol (Tetrahedron Letters, vol. 36, page 3323).
  • US Patent discloses mineral loaded chain-saturated hydrocarbon copolymer compositions containing a stabilizing amount of organo-silicon compound which is insoluble in water at 75°C and the process of preparing such a composition wherein said mineral-filled hydrocarbon is cured in the presence of a stabilizing amount of said organo-silicon compound.
  • a particularly preferred material is the polysiloxane obtained by hydrolyzing 2(1,3-butadienyl)dichloro(methyl)silane.
  • the object of the invention is to provide a 2-substituted-1,3-butadiene compound of the general formula (I) in which R 1 , R 2 and R 3 independently represent a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms provided that not all R 1 , R 2 and R 3 are lower alkyl groups having 1 to 5 carbon atoms.
  • the compounds of the formula (I) can be prepared by two different processes.
  • One of the processes comprises dehalogenating the halogen atoms at the 1 and 4 positions of a 2-substituted-1,4-dehalogeno-2-butene of the following formula (II) in which R 1 , R 2 and R 3 have the same meanings as defined above, and X represents a halogen, in a non- alcoholic solvent, e.g. a cyclic ether, thereby obtaining the compound of the formula (I).
  • a non- alcoholic solvent e.g. a cyclic ether
  • the compound of the formula (I) in which at least one of the three substituents is a halogen and the other substituents are independently a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms, the following sequence of reactions are used.
  • the more specified compound is represented by the following formula (la) in which at least one of A 1 , A 2 and A 3 represents a halogen and the others independently represents a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms.
  • This compound (la) is prepared by a procedure which comprises the steps of reacting 1,4-dihalogeno-2-butyne of the formula (III) in which X represents a halogen, with a compound of the formula (IV)
  • a 1 , A 2 and A 3 represents a halogen and the others independently represents a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms, thereby obtaining a compound of the formula (Ila) in which X, A 1 , A 2 and A3 have the same meanings as defined above, respectively, and subjecting the compound of the formula (Ila) to dehalogenation of the halogen atoms at the 1 and 4 positions thereof to obtain the compound of the above formula (la).
  • the compound of the formula (la) may be further reacted with a lower alcohol preferably in the presence of a base such as triethylamine to obtain a 2-substituted-1,3-butadiene compound of the following formula (lb) in which at least one of R 1' , R 2' and R 3 ' represents a lower alkoxy group having 1 to 5 carbon atoms, and the others represent a lower alkyl group having 1 to 5 carbon atoms.
  • a base such as triethylamine
  • the compound of the formula (lb) may be prepared by another procedure which comprises, after formation of the compound of the formula (Ila), reacting the compound of the formula (Ila) with a lower alcohol so that the halogen atoms joined to the silicon atom at the 2 position of the compound are substituted with lower alkoxy groups having 1 to 5 carbon atoms to give a compound of the following formula (IIb) in which R 1' , R 2' , R 3' and X have the same meanings as defined before, and subjecting the compound (IIb) to dehalogenation of halogens at the 1 and 4 positions thereof, thereby obtaining the compound of the above formula (lb).
  • a magnesium 2-substituted-1,3-butadienylhalide of the following formula (V) in which X represents a halogen is reacted with a silane compound of the general formula (VI) in which R 1 , R 2 and R 2 have the same meanings as defined before, respectively, i.e. they independently represent a halogen, a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms except that R 1 , R 2 and R 3 are all a lower alkyl group having 1 to 5 carbon atoms and R 4 represents a halogen or lower alkoxy group having 1 to 5 carbon atoms thereby obtaining the compound of the formula (I).
  • This process is economically advantageous because 2-substitued-1,3-butadienyl magnesium halide compounds and silane compounds, which can be readily prepared, are used as the starting materials, the control of the reaction is easy, and the number of reaction steps is small.
  • novel 2-substitued-1,3-butadiene compounds of the formula (I) according to the invention include 2-(trimethoxy)silyl-1,3-butadiene, 2-(methoxydimethyl)silyl-1,3-butadiene, 2-(dimethoxymethyl)-1,3-butadiene, 2-(trichloro)silyl-1,3-butadiene, 2-(dimethylchloro)silyl-1,3-butadiene, and the like.
  • the lower alkyl group and the lower alkoxy group have 1 to 5 carbon atoms respectively and the halogen include chlorine, bromine and iodine.
  • the compounds of the formula (I) may be prepared, according to one of the processes of the invention, from starting 1,4-dihalogeno-2-butene compounds of the formula (Ila) which have, at the 2 position, a silyl group having at least one halogen substituent.
  • the compounds of the formula (IIa) are prepared according to the following reaction formula A in which 1,4-dihalogeno-2-butyne compounds (III) are reacted with hydrosilanes of the formula (IV) having at least one halogen atom.
  • X represents a halogen
  • at least one of A 1 , A 2 and A3 represents a halogen
  • the others independently represent a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms.
  • 1,4-dihalogeno-2-butene are 1,4-dichloro-2-butene.
  • the above reaction is carried out in the absence of any solvents but using, as a catalyst, chloroplatinic acid dissolved in a solvent such as isopropyl alcohol.
  • the reaction temperature for the reaction A is from room temperature to a boiling point of a hydrosilane used, The reaction temperature is generally from about 30 minutes to 8 hours.
  • the compound of the formula (Ila) is dehalogenated in a non-alcoholic solvent according to the following reaction formula B.
  • the compound of the formula (la) may be further reacted with a lower alcohol having 1 to 5 carbon atoms preferably in the presence of a base according to the following reaction formula C, so that the halogen atom or atoms joined to the silicon atom at the 2 position of the compound are substituted with a lower alkoxy group having 1 to 5 carbon atoms to obtain a compound of the following formula (lb).
  • a 1 , A 2 and A3 is a halogen
  • the others independently represent a lower alkyl group having 1 to 5 carbon atoms, or a lower alkoxy group having 1 to 5 carbon atoms
  • at least one of R 1' , R 2' and R 3' represents a lower alkoxy group having 1 to 5 carbon atoms
  • the others independently represent a lower alkyl group, as defined before.
  • the compound of the formula (lb) may be prepared according to the following reaction formula D.
  • the reaction formula D the compound of the formula (Ila) is reacted with a lower alcohol preferably in the presence of a base to form a compound of the formula (IIb) in which the halogen atom jointed to the silicon atom at the 2 position thereof is substituted with the lower alkoxy group having 1 to 5 carbon atoms, followed by dehalogenation in nonalcoholic solvent to obtain a compound of the formula (lb).
  • at least one of R 1' , R 21 and R 3 ' represents a lower alkoxy group having 1 to 5 carbon atoms, and the others represent a lower alkyl group having 1 to 5 carbon atoms.
  • the nonalcoholic solvents used for the dehalogenation reaction include, for example, cyclic ethers. Specific and preferable examples of such ethers include tetrahydrofuran (THF), dioxane and the like.
  • THF tetrahydrofuran
  • zinc powder or the like it is preferable to use zinc powder in combination with a zinc salt such as zinc chloride.
  • the dehalogenation reaction is conducted at a temperature of from -10°C to a boiling point of non-alcoholic solvent used for a time of from 30 miutes to 8 hours.
  • the amount of the non- alcoholic solvent is preferably in the range of 3 to 10 mols per mol of the starting compound.
  • the reaction of substituting a halogen atom joined to the silicon atom with a lower alkoxy group having 1 to 5 carbon atoms, by reaction between a halogen and a lower alcohol proceeds smoothly when using a base, e.g. an organic aliphatic amine such as triethylamine.
  • the substitution reaction is conducted under conditions of a reaction temperature of from -10°C to 100°C and a reaction time of from 30 minutes to 2 hours.
  • the amount of the lower alcohol is in the range of from 1.0 to 1.5 mols per mol of the starting compound and the amount of the amine is in the range of from 1.0 to 1.5 mols per mol of the starting material.
  • reaction product obtained in one step may be used, as it is, in a subsequent step.
  • 1,4-dichloro-2-butene- having at least one halogen-substituted silyl group at the 2 position thereof or 1,3-butadiene having at least one halogen-substituted silyl group at the 2 position may be readily introduced, at the silyl group, with various substituents other than lower alkyl group having 1 to 5 carbon atoms, and lower alkoxy group having 1 to 5 carbon atoms by the use of the reactivity of the halogen of the halogen-substituted silyl group.
  • This process comprises reaction between magnesium 2-substituted-1,3-butadienyl halide of the formula (V) and a silane compound of the formula (VI) according to the following reaction formula (E).
  • X represents a halogen
  • R 1 , R 2 and R 3 independently represent a lower alkyl group having 1 to 5 carbon atoms or a lower alkoxy group having 1 to 5 carbon atoms except the case where R 1 , R 2 and R 3 are all a lower alkyl group having 1 to 5 carbon atoms
  • R 4 represents a halogen or a lower alkoxy group having 1 to 5 carbon atoms.
  • magnesium 2-substitued-1,3-butadienyl halide of the formula (V) include Grignard reagents resulting from compounds such as of chloroprene, bromoprene, 2,3-dichloro-1,3-butadiene, and so on. These Grignard reagents may be prepared by any ordinary procedures such as described, for example, in "Journal of Organic Chemistry, vol. 44, page 4788 (1979)".
  • the silane compound of the formula (VI) are, for example, tetramethoxysilane, tetrabutoxysilane, trimethoxychlorosilane, tributoxybromosilane, trimethoxymethylsilane, tributoxybutylsilane, dimethoxydichlorosilane, dibutoxydibromosilane, dimethoxydimethylsilane, dibutoxydibutylsilane, dimethoxymethylchlorosilane, dibutoxybutylbromosilane, methoxytrichlorosilane, butoxytribromosilane, butoxydichloromethylsilane, butoxydibromobutylsilane, methoxychlorodimethylsilane, butoxybromodibutylsilane, tetrachlorosilane, tetrabromosi lane, trichloromethylsilane, tribromobutylsilane
  • the reaction between the Grignard reagent of the formula (V) and the silane compound of the formula (VI) is carried out by procedure which comprises dissolving the Grignard reagent in a solvent such as tetrahydrofuran, preferably cooling the solution to below room temperature, and subjecting to reaction with the silane compound in an atmosphere of an inert gas.
  • the reaction temperature is preferably in the range of -50°C to a boiling point of the solvent used, most preferably in the range of 0°C to room temperature.
  • the reaction time is in the range of from 10 minutes to 5 hours, preferably from 30 minutes to 2 hours.
  • the molar ratio of the Grignard reagent and the silane compound is from 1:0.2 to 1:5, preferably from 1:1 to 1:2.
  • reaction solution is conveniently determined in view of the heat of reaction and the volumetric efficiency.
  • the reaction between the Grignard reagent and the silane compound is ordinarily caused to proceed in an atmosphere of an inert gas.
  • inert gas examples include argon, helium, nitrogen and the like, which may be used singly or in combination. Of these, argon is preferred.
  • the compound of the formula (la) is reacted with a lower alcohol according to the reaction formula (C), as indicated before, preferably in the presence of a base including an organic aliphatic amine such as triethylamine in a nonalcoholic solvent such as tetrahydrofuran, by which the reaction proceeds smoothly.
  • a base including an organic aliphatic amine such as triethylamine in a nonalcoholic solvent such as tetrahydrofuran
  • the halogen atom joined to the silane group is readily substituted with a lower alkoxy group having 1 to 5 carbon atoms to give the compound of the formula (lb) according to the following reaction formula (F).
  • a 1 , A 2 , A3 and R 4 have, respectively, the same meanings as defined above.
  • the reaction can be easily controlled with a reduced number of steps, so that substituted-1,3-butadiene derivatives can be economically prepared.
  • the solvent was distilled off under reduced pressure at a low temperature of -20°C and the residue was subjected to the bulb-to-bulb distillation to obtain 3.1 g of 2-(dimethylchloro)silyl-1,3-butadiene.
  • the content of the product was determined as follows: the magnesium 2-(1,3-butadienyl)chloride was hydrolyzed using water and an excess of hydrochloric acid, followed by back titration of the hydrochloric acid with an aqueous caustic soda solution.

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Claims (11)

1. 1,3-butadiène substitué en position 2, de formule générale (I)
Figure imgb0060
dans laquelle R1, R2 et R3 représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, étant entendu que R1, R2 et R3 ne sont pas tous des groupes alkyle inférieurs ayant de 1 à 5 atomes de carbone.
2. Procédé pour la préparation d'un 1,3-butadiène substitué en position 2, de formule générale (I)
Figure imgb0061
dans laquelle R1, R2 et R3 représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, étant entendu que R1, R2 et R3 ne sont pas tous des groupes alkyle inférieurs ayant de 1 à 5 atomes de carbone, procédé comprenant l'exposition d'un 1,4-dihalogéno-2-butène substitué en position 2, de formule générale (II)
Figure imgb0062
dans laquelle R1, R2 et R3 ont, respectivement, les mêmes significations que celles données plus haut, et X représente un halogène, à une déshalogénation avec élimination des atomes d'halogène en positions 1 et 4 de celui-ci, dans un solvant non alcoolique.
3. Procédé selon la revendication 2, dans lequel le solvant non alcoolique est un éther cyclique.
4. Procédé pour la préparation d'un 1,3-butadiène substitué en position 2, de formule générale (Ib) suivante
Figure imgb0063
dans laquelle au moins l'un des radicaux R1', R2' et R3' représente un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone et les autres représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone, procédé comprenant la mise en réaction d'un composé de formule générale (la)
Figure imgb0064
dans laquelle au moins l'un parmi A1, A2 et A3 représente un halogène et les autres représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, avec un alcool inférieur, ce par quoi l'atome d'halogène lié à l'atome de silicium en position 2 est remplacé par un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone.
5. Procédé selon la revendication 4, dans lequel on fait réagir le composé de formule (la) avec un alcool inférieur, en présence d'une base.
6. Procédé selon la revendication 5, dans lequel la base est une amine organique.
7. Procédé selon la revendication 6, dans lequel l'amine organique est la triéthylamine.
8. Procédé pour la préparation d'un 1,3-butadiène substitué en position 2, de formule (Ib)
Figure imgb0065
dans laquelle au moins l'un des radicaux R1', R2' et R3' représente un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone et les autres représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone, procédé comprenant la mise en réaction d'un 1,4-dihalogéno-2-butyne de formule générale (III)
Figure imgb0066
dans laquelle X représente un halogène, avec un composé de formule générale (IV)
Figure imgb0067
dans laquelle au moins l'un parmi A1, A et A3 représente un halogène et les autres représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, pour l'obtention d'un composé de formule générale (IIa)
Figure imgb0068
dans laquelle X, A1, A2 et A3 ont, respectivement, les mêmes significations que celles données plus haut; la réaction du composé de formule (Ila) avec un alcool inférieur, pour l'obtention d'un composé de formule générale (llb) dans lequel l'atome d'halogène lié à l'atome de silicium en position 2 est remplacé par un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone
Figure imgb0069
dans laquelle R1', R2', R3' et X sont, respectivement, tels que définis précédemment; et l'exposition du composé de formule (Ilb) à une déshalogénation, pour l'obtention du composé de formule générale (Ib) donnée plus haut.
9. Procédé pour la préparation d'un 1,3-butadiène substitué en position 2, de formule générale (I)
Figure imgb0070
dans laquelle R1, R2 et R3 représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, étant entendu que R1, R2 et R3 ne sont pas tous des groupes alkyle inférieurs ayant de 1 à 5 atomes de carbone, procédé comprenant la mise en réaction d'un halogénure de 1,3-butadiényle substitué en position 2 par du magnésium, de formule générale (V)
Figure imgb0071
dans laquelle X représente un halogène, avec un silane de formule générale (VI)
Figure imgb0072
dans laquelle R1, R2 et R3 ont respectivement les mêmes significations que celles données plus haut, et R4 représente un halogène ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone.
10. Procédé selon la revendication 9, dans lequel le composé de formule (V) est le chlorure de 1,3-butadiényi-2-magnésium.
11. Procédé pour la préparation d'un 1,3-butadiène substitué en position 2, de formule générale (Ib)
Figure imgb0073
dans laquelle au moins l'un des radicaux R1', R2', R3' représente un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone et les autres représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone, procédé comprenant la mise en réaction d'un halogénure de 1,3-butadiényle substitué en position 2 par du magnésium, de formule (V)
Figure imgb0074
dans laquelle X représente un halogène, avec un silane de formule (Vla)
Figure imgb0075
dans laquelle au moins l'un parmi A1, A2 et A3 représente un halogène et les autres représentent indépendamment un groupe alkyle inférieur ayant de 1 à 5 atomes de carbone ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, et R4 représente un halogène ou un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, pour l'obtention d'un composé de formule (la)
Figure imgb0076
dans laquelle A1, A2 et A3 ont, respectivement, les mêmes significations que celles données plus haut; et ensuite la mise en réaction du composé de formule (la) avec un alcool inférieur ayant de 1 à 5 atomes de carbone, ce par quoi l'atome d'halogène lié à l'atome de silicium en position 2 est remplacé par un groupe alcoxy inférieur ayant de 1 à 5 atomes de carbone, pour l'obtention du composé de formule générale (Ib)
Figure imgb0077
telle que définie plus haut.
EP85101980A 1984-02-24 1985-02-22 Dérivés de 1,3-butadiène 2-substituée et procédé de leur préparation Expired - Lifetime EP0154867B1 (fr)

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JP33733/84 1984-02-24
JP59033733A JPS60197694A (ja) 1984-02-24 1984-02-24 ２−置換−１，３−ブタジエン誘導体及びその製造法
JP277154/84 1984-12-25
JP27715484A JPS61151196A (ja) 1984-12-25 1984-12-25 置換−１，３−ブタジエン誘導体の製造法

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US4677216A (en) 1987-06-30
EP0154867A1 (fr) 1985-09-18
DE3577439D1 (de) 1990-06-07

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